The effect of synthesis parameters on the microstructural behavior and morphology during the yttrium oxide (Y 2 O 3 ) formation is reported. Y 2 O 3 crystals were produced by a modified sol-gel route assisted by polyvinyl alcohol solution varying the calcination temperature and solution pH. The crystalline phase formation was investigated using X-ray powder diffraction combined with the Rietveld refinement method. The microstructural properties were analyzed by using the Williamson-Hall formalism. The calcination temperature followed the thermal events observed in the differential thermal analysis combined with the thermogravimetric analysis of the precursor xerogel. It was seen that the combination of PVA and pH variation can be used to minimize the calcination time and temperature. The morphological analysis showed samples with different sizes and appearances depending on pH and calcination temperature. Therefore, it was shown that the parameters in the synthesis process can be used to tailor the properties of Y 2 O 3 , such as crystallite size, degree of structural ordering, and morphology, and consequently, improve the desired application.